EP3088436B1 - Laminate body - Google Patents
Laminate body Download PDFInfo
- Publication number
- EP3088436B1 EP3088436B1 EP14873530.1A EP14873530A EP3088436B1 EP 3088436 B1 EP3088436 B1 EP 3088436B1 EP 14873530 A EP14873530 A EP 14873530A EP 3088436 B1 EP3088436 B1 EP 3088436B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- thiol
- contained
- groups
- polythiol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000001875 compounds Chemical class 0.000 claims description 144
- 229920001971 elastomer Polymers 0.000 claims description 98
- 239000005060 rubber Substances 0.000 claims description 98
- 239000000203 mixture Substances 0.000 claims description 89
- 229920006295 polythiol Polymers 0.000 claims description 79
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 77
- -1 thioglycolic acid ester Chemical class 0.000 claims description 63
- 125000003700 epoxy group Chemical group 0.000 claims description 60
- 239000004593 Epoxy Substances 0.000 claims description 40
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 150000003573 thiols Chemical class 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N alpha-mercaptoacetic acid Natural products OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 claims description 7
- 150000002978 peroxides Chemical class 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000003944 halohydrins Chemical class 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 150000004985 diamines Chemical group 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 description 94
- 239000000853 adhesive Substances 0.000 description 92
- 150000003254 radicals Chemical class 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 20
- 244000043261 Hevea brasiliensis Species 0.000 description 19
- 229920003052 natural elastomer Polymers 0.000 description 19
- 229920001194 natural rubber Polymers 0.000 description 19
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 16
- 125000005842 heteroatom Chemical group 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 239000004636 vulcanized rubber Substances 0.000 description 11
- 125000001931 aliphatic group Chemical group 0.000 description 10
- 239000002174 Styrene-butadiene Substances 0.000 description 9
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000032798 delamination Effects 0.000 description 6
- 150000001451 organic peroxides Chemical class 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000007788 roughening Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 3
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 238000006596 Alder-ene reaction Methods 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 2
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 1
- CTPYJEXTTINDEM-UHFFFAOYSA-N 1,2-bis(1-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOCC(C)C1=CC=CC=C1C(C)COOC(C)(C)C CTPYJEXTTINDEM-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- YGKHJWTVMIMEPQ-UHFFFAOYSA-N 1,2-propanedithiol Chemical compound CC(S)CS YGKHJWTVMIMEPQ-UHFFFAOYSA-N 0.000 description 1
- CNAIYFIVNYOUFM-UHFFFAOYSA-N 1,3-bis(4-methoxyphenyl)propane-2,2-dithiol Chemical compound C1=CC(OC)=CC=C1CC(S)(S)CC1=CC=C(OC)C=C1 CNAIYFIVNYOUFM-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- KADZDOLYFZTSSM-UHFFFAOYSA-N 1,3-diphenylpropane-2,2-dithiol Chemical compound C=1C=CC=CC=1CC(S)(S)CC1=CC=CC=C1 KADZDOLYFZTSSM-UHFFFAOYSA-N 0.000 description 1
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 1
- PGTWZHXOSWQKCY-UHFFFAOYSA-N 1,8-Octanedithiol Chemical compound SCCCCCCCCS PGTWZHXOSWQKCY-UHFFFAOYSA-N 0.000 description 1
- TWWSEEHCVDRRRI-UHFFFAOYSA-N 2,3-Butanedithiol Chemical compound CC(S)C(C)S TWWSEEHCVDRRRI-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- YZIGUJRGKPNSGI-UHFFFAOYSA-N 2-[2,3-bis(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=CC(CCS)=C1CCS YZIGUJRGKPNSGI-UHFFFAOYSA-N 0.000 description 1
- HVVRGPYMAUJRKF-UHFFFAOYSA-N 2-[2-(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=CC=C1CCS HVVRGPYMAUJRKF-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- BXYWKXBAMJYTKP-UHFFFAOYSA-N 2-[2-[2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethoxy]ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOCCOCCOC(=O)CCS BXYWKXBAMJYTKP-UHFFFAOYSA-N 0.000 description 1
- YIMJMXYFLBUNMH-UHFFFAOYSA-N 2-[3,4-bis(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=C(CCS)C(CCS)=C1 YIMJMXYFLBUNMH-UHFFFAOYSA-N 0.000 description 1
- GFSULDUIAFNGRB-UHFFFAOYSA-N 2-[3,5-bis(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC(CCS)=CC(CCS)=C1 GFSULDUIAFNGRB-UHFFFAOYSA-N 0.000 description 1
- RKPZXQVJXKNNSB-UHFFFAOYSA-N 2-[3-(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=CC(CCS)=C1 RKPZXQVJXKNNSB-UHFFFAOYSA-N 0.000 description 1
- PESHQGQMMIRLMA-UHFFFAOYSA-N 2-[4-(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=C(CCS)C=C1 PESHQGQMMIRLMA-UHFFFAOYSA-N 0.000 description 1
- HIGURUTWFKYJCH-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxymethyl)cyclohexyl]methoxymethyl]oxirane Chemical compound C1OC1COCC1(COCC2OC2)CCCCC1 HIGURUTWFKYJCH-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- RFMXKZGZSGFZES-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS.OC(=O)CS.CCC(CO)(CO)CO RFMXKZGZSGFZES-UHFFFAOYSA-N 0.000 description 1
- QNQBPLJBKMDKLK-UHFFFAOYSA-N 2-methylbenzene-1,4-dithiol Chemical compound CC1=CC(S)=CC=C1S QNQBPLJBKMDKLK-UHFFFAOYSA-N 0.000 description 1
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 1
- YMMLZUQDXYPNOG-UHFFFAOYSA-N 2-methylpentan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)CCCCCC(C)(C)C YMMLZUQDXYPNOG-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- RQPNXPWEGVCPCX-UHFFFAOYSA-N 3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O RQPNXPWEGVCPCX-UHFFFAOYSA-N 0.000 description 1
- IPNDIMIIGZSERC-UHFFFAOYSA-N 4-(2-sulfanylacetyl)oxybutyl 2-sulfanylacetate Chemical compound SCC(=O)OCCCCOC(=O)CS IPNDIMIIGZSERC-UHFFFAOYSA-N 0.000 description 1
- FOWDDWLRTIXWET-UHFFFAOYSA-N 4-[4-(4-sulfanylphenyl)pentan-2-yl]benzenethiol Chemical compound C=1C=C(S)C=CC=1C(C)CC(C)C1=CC=C(S)C=C1 FOWDDWLRTIXWET-UHFFFAOYSA-N 0.000 description 1
- NIAAGQAEVGMHPM-UHFFFAOYSA-N 4-methylbenzene-1,2-dithiol Chemical compound CC1=CC=C(S)C(S)=C1 NIAAGQAEVGMHPM-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- WFTJMDZONKZMPN-UHFFFAOYSA-N 6-(2-sulfanylacetyl)oxyhexyl 2-sulfanylacetate Chemical compound SCC(=O)OCCCCCCOC(=O)CS WFTJMDZONKZMPN-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GZPRASLJQIBVDP-UHFFFAOYSA-N CC(C)(C(CC1)CCC1OCC1OC1)C(CC1)CCC1OCC1OC1 Chemical compound CC(C)(C(CC1)CCC1OCC1OC1)C(CC1)CCC1OCC1OC1 GZPRASLJQIBVDP-UHFFFAOYSA-N 0.000 description 1
- SWONWHXYIBVJEK-QAIJIXMLSA-N CC(C)(C1)CC(C)(CN(C(N(CC(C)(C2)CC(C)(C)CC2NC(OC[C@@H]2OC2)=O)C(N2CC(C)(C3)CC(C)(C)CC3NC(OCC3OC3)=O)=O)=O)C2=O)CC1NC(OCCOC)=O Chemical compound CC(C)(C1)CC(C)(CN(C(N(CC(C)(C2)CC(C)(C)CC2NC(OC[C@@H]2OC2)=O)C(N2CC(C)(C3)CC(C)(C)CC3NC(OCC3OC3)=O)=O)=O)C2=O)CC1NC(OCCOC)=O SWONWHXYIBVJEK-QAIJIXMLSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- SDEFSQDZLUZWPW-UHFFFAOYSA-N [2,3-bis(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=CC(CS)=C1CS SDEFSQDZLUZWPW-UHFFFAOYSA-N 0.000 description 1
- NNJWFWSBENPGEY-UHFFFAOYSA-N [2-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=CC=C1CS NNJWFWSBENPGEY-UHFFFAOYSA-N 0.000 description 1
- OWDDXHQZWJBGMZ-UHFFFAOYSA-N [3,4-bis(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C(CS)=C1 OWDDXHQZWJBGMZ-UHFFFAOYSA-N 0.000 description 1
- STWRQBYJSPXXQE-UHFFFAOYSA-N [3,5-bis(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC(CS)=CC(CS)=C1 STWRQBYJSPXXQE-UHFFFAOYSA-N 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 1
- JSNABGZJVWSNOB-UHFFFAOYSA-N [3-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=CC(CS)=C1 JSNABGZJVWSNOB-UHFFFAOYSA-N 0.000 description 1
- IYPNRTQAOXLCQW-UHFFFAOYSA-N [4-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C=C1 IYPNRTQAOXLCQW-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- PPQNMKIMOCEJIR-UHFFFAOYSA-N benzene-1,2,3-trithiol Chemical compound SC1=CC=CC(S)=C1S PPQNMKIMOCEJIR-UHFFFAOYSA-N 0.000 description 1
- UKLXGHUHPLLTKD-UHFFFAOYSA-N benzene-1,2,4-trithiol Chemical compound SC1=CC=C(S)C(S)=C1 UKLXGHUHPLLTKD-UHFFFAOYSA-N 0.000 description 1
- KXCKKUIJCYNZAE-UHFFFAOYSA-N benzene-1,3,5-trithiol Chemical compound SC1=CC(S)=CC(S)=C1 KXCKKUIJCYNZAE-UHFFFAOYSA-N 0.000 description 1
- ZWOASCVFHSYHOB-UHFFFAOYSA-N benzene-1,3-dithiol Chemical compound SC1=CC=CC(S)=C1 ZWOASCVFHSYHOB-UHFFFAOYSA-N 0.000 description 1
- WYLQRHZSKIDFEP-UHFFFAOYSA-N benzene-1,4-dithiol Chemical compound SC1=CC=C(S)C=C1 WYLQRHZSKIDFEP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- SMTOKHQOVJRXLK-UHFFFAOYSA-N butane-1,4-dithiol Chemical compound SCCCCS SMTOKHQOVJRXLK-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- YKRCKUBKOIVILO-UHFFFAOYSA-N cyclohexane-1,2-dithiol Chemical compound SC1CCCCC1S YKRCKUBKOIVILO-UHFFFAOYSA-N 0.000 description 1
- UOQACRNTVQWTFF-UHFFFAOYSA-N decane-1,10-dithiol Chemical compound SCCCCCCCCCCS UOQACRNTVQWTFF-UHFFFAOYSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- KMTUBAIXCBHPIZ-UHFFFAOYSA-N pentane-1,5-dithiol Chemical compound SCCCCCS KMTUBAIXCBHPIZ-UHFFFAOYSA-N 0.000 description 1
- UKQMUPLYHOXQQR-UHFFFAOYSA-N phenylmethanedithiol Chemical compound SC(S)C1=CC=CC=C1 UKQMUPLYHOXQQR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- HMPSOEYFMTWOFC-UHFFFAOYSA-N propane-2,2-dithiol Chemical compound CC(C)(S)S HMPSOEYFMTWOFC-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/04—Epoxynovolacs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
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- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/12—Layered products comprising a layer of natural or synthetic rubber comprising natural rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2319/00—Synthetic rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2363/00—Epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2405/00—Adhesive articles, e.g. adhesive tapes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31515—As intermediate layer
Definitions
- the present invention relates to a composition, an adhesive and a layered body, and more specifically relates to a composition and an adhesive that are suitable for adhesion to rubber, and a layered body in which a rubber layer is adhered using the composition.
- JP-A Japanese Patent Application Laid-open
- JP-A No. H10-139901 vulcanized rubber is surface-treated, and another member is adhered to the surface-treated face using an adhesive.
- JP2001-131262 discloses an adhesive composition and its application to concrete and cement, but not to rubber layers.
- JP-A No. H10-139901 includes adhering vulcanized rubber to another member using a polyurethane-based adhesive. However, there is still a room for improvement of adhesive power thereof.
- an object of the present invention is to provide a composition capable of exhibiting high adhesive power to rubber, and a layered body in which a rubber layer and an adhesion layer formed using the composition are adhered.
- a a layered body is provided according to claim 1.
- an adhesive that includes the above-described composition is provided.
- a layered body which includes, in this order, a rubber layer, an adhesion layer formed using the composition of any one of [1] to [3], and another layer.
- the present invention it is possible to provide a composition capable of exhibiting high adhesive power to rubber, and a layered body in which a rubber layer and an adhesion layer formed using the composition are adhered.
- composition used in the present invention is a composition as in claim 1.
- composition used in the present invention is able to exhibit a high adhesive power to rubber. Further, the composition used in the present invention is able to exhibit a high adhesive power to vulcanized rubber as well as to unvulcanized rubber. Although the reason therefor is not clear, it is presumed that the following may be the reason.
- the composition used in the present invention strongly hardens through an anionic polymerization reaction between a part of the amount of the polythiol compound (A) and the compound (B) having plural epoxy groups.
- An adhesion layer formed using the composition used in the present invention thereby may acquire sufficient film strength, conceivably due to the strong hardening.
- polythiol compound (A) becomes a thiyl radical as a result of the radical generator (C) that has been activated by energy, such as heat or light.
- energy such as heat or light.
- the so-formed thiyl radical reacts with a carbon-carbon double bond present in rubber.
- the composition used in the present invention exhibits high interfacial adhesive power to rubber, conceivably because the composition according to the present invention chemically binds to rubber through the thiol-ene reactions as described above.
- the composition used in the present invention exhibits high interfacial adhesive power to vulcanized rubber as well as to unvulcanized rubber, conceivably because carbon-carbon double bonds are present not only in unvulcanized rubber but also in vulcanized rubber.
- an adhesion layer having both high interfacial adhesive power to rubber and high film strength can be formed using the composition used in the present invention. Therefore, when a composition used in the present invention is used as an adhesive, high adhesive power to an adherend (particularly, rubber) can be exhibited.
- composition used in the present invention is able to exhibit adhesive power to rubber even when carbon-carbon double bonds are not necessarily present in the rubber.
- composition enables sufficiently high adhesive power to be exhibited with respect to rubbers in general, even in the case where surface roughening treatment, such as grinding, is not carried out on the surfaces of the adhesion faces of the rubbers, conceivably because the composition and the rubber chemically bind to each other as described above. Omitting a surface roughening treatment on the adhesion face of the rubber, as described above, provides for simplification and improved efficiency of an adhesion process.
- surface roughening treatment may be carried out on the surface on the adhesion face of the rubber, thereby improving the adhesive power via the utilization of an anchor effect.
- composition used in the present invention is able to exhibit high adhesive power to vulcanized rubber, adhesion can be achieved at a remarkably lower temperature and over a remarkably shorter length of time (for example, from 100 to 150°C for from 3 to 30 minutes) than when unvulcanized rubber materials are brought into contact with each other and adhesion is performed while vulcanizing them.
- the polythiol compound (A), the compound (B) having plural epoxy groups, the radical generator (C), the amine-based catalyst (D), and the after-mentioned surface adjustor (E) are also referred to as "component (A)", “component (B)”, “component (C)”, “component (D)”, and “component (E)", respectively, in some cases.
- polythiol compound refers to a compound having two or more thiol groups in one molecule thereof.
- component (A) one polythiol compound may be used singly, or two or more polythiol compounds may be used in combination.
- the number of thiol groups in one molecule thereof is not particularly limited as long as the above-defined relationship with the total molar number of epoxy groups in the component (B) is satisfied. From the viewpoint of improving the adhesive power, the polythiol compound (A) preferably has three or more thiol groups in one molecule thereof.
- the upper limit of the number of thiol groups in one molecule of the polythiol compound (A) is not particularly limited, and may be selected, as appropriate, as long as the effects according to the present invention are not impaired.
- the number of thiol groups in one molecule of the polythiol compound (A) may be appropriately selected within the range of usually from 2 to 7, preferably from 3 to 6, and more preferably from 3 to 4, although the number may vary depending on whether the polythiol compound (A) is a low-molecular-weight compound or a high-molecular-weight compound. However, these ranges should not be construed as limiting the scope of the present invention.
- polythiol compound (A) encompasses primary thiols, secondary thiols, and tertiary thiols.
- Primary thiols are preferable from the viewpoint of improving the adhesive power.
- the molecular weight of the polythiol compound (A) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, further more preferably 900 or less, and particularly preferably 800 or less, from the viewpoint of improving the adhesive power. Further, the lower limit of the molecular weight of the polythiol compound (A) is not particularly limited. The lower limit of the molecular weight of the polythiol compound (A) is preferably 200 or more, and still more preferably 300 or more. When the polythiol compound (A) is a polymer, the "molecular weight" refers to the styrene-equivalent number average molecular weight.
- Examples of the polythiol compound (A) include an aliphatic polythiol that may include a heteroatom and an aromatic polythiol that may include a heteroatom.
- An aliphatic polythiol that may include a heteroatom is preferable from the viewpoint of improving the adhesive power.
- aliphatic polythiol that may include a heteroatom refers to an aliphatic compound that has two or more thiol groups in one molecule thereof and that may include a heteroatom.
- aromatic polythiol that may include a heteroatom refers to an aromatic compound that has two or more thiol groups in one molecule thereof and that may include a heteroatom.
- the included heteroatom, or heteroatoms is preferably at least one kind selected from the group consisting of oxygen, nitrogen, sulfur, phosphorus, halogen, and silicon; is more preferably at least one kind selected from the group consisting of oxygen, nitrogen, sulfur, phosphorus, and halogen; and is particularly preferably at least one kind selected from the group consisting of oxygen, nitrogen, and sulfur.
- Examples of the aliphatic polythiol that may include a heteroatom include: a polythiol in which the portion other than the thiol groups is an aliphatic hydrocarbon, such as an alkanedithiol having from 2 to 20 carbon atoms; a polythiol obtainable by replacing halogen atoms of a halohydrin adduct of an alcohol by thiol groups; a polythiol that is a hydrogen sulfide reaction product of a polyepoxide compound; a thioglycolic acid ester obtainable by an ester-forming reaction between a polyhydric alcohol having from 2 to 6 hydroxyl groups in a molecule thereof and thioglycolic acid; a mercapto fatty acid ester obtainable by an ester-forming reaction between a polyhydric alcohol having from 2 to 6 hydroxyl groups in a molecule thereof and a mercapto fatty acid; a thiol isocyanurate compound obtainable by
- polyhydric alcohol having from 2 to 6 hydroxyl groups in a molecule thereof examples include an alkanediol having from 2 to 20 carbon atoms, a poly(oxyalkylene)glycol, glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.
- aliphatic polythiols that may include a heteroatom
- a thiol that does not include a polysulfide group or a siloxane bond is also preferable.
- the polythiol in which the portion other than thiol groups is an aliphatic hydrocarbon is, for example, an alkanedithiol having from 2 to 20 carbon atoms.
- alkanedithiol having from 2 to 20 carbon atoms examples include 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 1-1-cyclohexanedithiol, and 1,2-cyclohexanedithiol.
- thioglycolic acid ester examples include 1,4-butanediol bisthioglycolate, 1,6-hexanediol bisthioglycolate, trimethylolpropane tristhioglycolate, and pentaerythritol tetrakisthioglycolate.
- the mercapto fatty acid ester is preferably a ⁇ -mercapto fatty acid ester having a primary thiol group, and is more preferably a ⁇ -mercaptopropionic acid ester of a polyhydric alcohol having from 2 to 6 hydroxyl groups in a molecule thereof, from the viewpoint of improving the adhesive power.
- the mercapto fatty acid ester having a primary thiol group preferably has from 4 to 6 thiol groups in one molecule thereof, more preferably has 4 or 5 thiol groups in one molecule thereof, and further preferably has 4 thiol groups in one molecule thereof, from the viewpoint of improving the adhesive power.
- ⁇ -mercaptopropionic acid ester having a primary thiol group examples include tetraethyleneglycol bis(3-mercaptopropionate) (EGMP-4), trimethylolpropane tris(3-mercaptopropionate) (TMMP), pentaerythritol tetrakis(3-mercaptopropionate) (PEMP), and dipentaerythritol hexakis(3-mercaptopropionate) (DPMP).
- EGMP-4 tetraethyleneglycol bis(3-mercaptopropionate)
- TMMP trimethylolpropane tris(3-mercaptopropionate)
- PEMP pentaerythritol tetrakis(3-mercaptopropionate)
- DPMP dipentaerythritol hexakis(3-mercaptopropionate)
- PEMP and DPMP are preferable, and PEMP is more preferable
- the ⁇ -mercaptopropionic acid ester having a secondary thiol group is, for example, an ester between a polyhydric alcohol having from 2 to 6 hydroxyl groups in a molecule thereof and ⁇ -mercaptobutanoic acid, and specific examples thereof include 1,4-bis(3-mercaptobutylyloxy)butane and pentaerythritol tetrakis(3-mercaptobutyrate).
- the thiol isocyanurate compound which is obtainable via a reaction between an isocyanurate compound and a thiol, is preferably a thiol isocyanurate compound having a primary thiol group, from the viewpoint of improving the adhesive power.
- the thiol isocyanurate compound having a primary thiol group preferably has 2 to 4 thiol groups in one molecule thereof, and more preferably has 3 thiol groups in one molecule thereof, from the viewpoint of improving the adhesive power.
- the thiol isocynaurate compound having a primary thiol group is preferably tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (TEMPIC).
- silicone modified with thiol groups examples include mercapto-modified silicone oils such as KF-2001, KF-2004, and X-22-167B (tradenames, manufactured by Shin-etsu Chemical Co., Ltd.), SMS042 and SMS022 (tradenames, manufactured by Gelest Inc.), and PS849 and PS850 (tradenames, manufactured by UCT Inc.).
- aromatic polythiols examples include the aromatic polythiols exemplified below. As described above, the aromatic polythiol may include a heteroatom. Specifically, examples of the aromatic polythiols include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1,2,4-tris(mer
- the term "compound having plural epoxy groups” refers to a compound having two or more epoxy groups in one molecule thereof.
- the component (B) one compound having plural epoxy groups may be used singly, or two or more compounds each having plural epoxy groups may be used in combination.
- the number of epoxy groups in one molecule thereof is not particularly limited, as long as the above-defined relationship with the total molar number of thiol groups of the component (A) is satisfied. From the viewpoint of improving the adhesive properties and the durability of adhesion, the number of epoxy groups in one molecule of the component (B) may be determined, as appropriate, within a range of usually 2 or more, although the number may vary depending on whether the component (B) is a low-molecular-weight compound or a high-molecular-weight compound.
- the epoxy equivalent weight of the compound (B) having plural epoxy groups is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, further more preferably 900 or less, and particularly preferably 800 or less, from the viewpoint of improving the adhesive properties.
- the lower limit of the molecular weight of the component (B) is not particularly limited, and is preferably, for example, 50 or more, and more preferably 100 or more.
- the "molecular weight" refers to the styrene-equivalent number average molecular weight.
- Examples of the compound (B) having plural epoxy groups include an aromatic epoxide, an aliphatic epoxide, an alicyclic epoxide, and modified products thereof.
- an aromatic epoxide having a ring structure other than a glycidyl group, an alicyclic epoxide having a ring structure other than a glycidyl group, and modified products thereof are preferable.
- the aromatic epoxide preferably has two or more aromatic rings.
- the alicyclic epoxide preferably has three or more aliphatic rings.
- aromatic epoxide examples include: bisphenol-type aromatic epoxides such as a bisphenol A-type epoxy compound, a bisphenol F-type epoxy compound, and a bisphenol S-type epoxy compound; novolac resin-type aromatic epoxides such as a phenol novolac-type epoxy compound and a cresol novolac-type epoxy compound; and other aromatic epoxides such as a polyphenol-type epoxy compound, a biphenyl-type epoxy compound, a naphthalene ring-containing epoxy compound, and a fluorene-type epoxy compound.
- the aromatic epoxide may have a urethane skeleton.
- aliphatic epoxide examples include a polyalkyleneglycol diglycidyl ether such as trimethylolpropane triglycidyl ether, and a polyglycidyl ether of a polyhydric alcohol such as glycerin.
- the alicyclic epoxide is, for example, an alicyclic epoxide such as cyclohexane dimethanol diglycidyl ether.
- the alicyclic epoxide may have a urethane skeleton.
- Modified products of the aromatic, aliphatic or alicyclic epoxide include modified products of aromatic epoxides such as a hydrogenated bisphenol A-type epoxy compound, a hydrogenated bisphenol F-type epoxy compound, a hydorgenated biphenyl-type epoxy compound, and a brominated bisphenol-type epoxy compound.
- a cresol novolac-type epoxy compound for example, JER152 (tradename, manufactured by Mitsubishi Chemical Corporation), which is the following epoxy compound B-1), a bisphenol A-type epoxy compound (for example JER1001B80 (tradename, manufactured by Mitsubishi Chemical Corporation), which is the following epoxy compound B-2, or EP-4100 (tradename, manufactured by ADEKA Corporation), which is the following epoxy compound B-3), an aromatic epoxide having a urethane skeleton (for example, the following epoxy compound B-4), an alicyclic epoxide having a urethane skeleton (for example, the following epoxy compound B-5), and a hydrogenated bisphenol A-type epoxy compound (for example, EPOLIGHT4000 (tradename, manufactured by KYOEISHA CHEMICAL Co., Ltd.), which is the following epoxy compound B-6) are preferable.
- JER152 tradename, manufactured by Mitsubishi Chemical Corporation
- B-1 bisphenol A-type epoxy compound
- JER1001B80 tradename, manufactured by Mitsubishi Chemical Corporation
- epoxy compound B-4 illustrated above can be synthesized in the following manner. Specifically, epoxy compound B-4 can be synthesized by adding, at 70°C, glycidol (for example, a product manufactured by Junsei Chemical Co., Ltd.) to an isocyanate oligomer having a TDI adduct structure (for example, DESMODUR L-75 (tradename) manufactured by Bayer) such that the number of NCO groups becomes the same as the number of OH groups, and further adding a tin-based catalyst (for example, NEOSTANN U-100 (tradename) manufactured by Nitto Kasei Co., Ltd.) in an amount of 0.05% by mass.
- glycidol for example, a product manufactured by Junsei Chemical Co., Ltd.
- an isocyanate oligomer having a TDI adduct structure for example, DESMODUR L-75 (tradename) manufactured by Bayer
- epoxy compound B-5 illustrated above can be synthesized in the following manner. Specifically, epoxy compound B-5 can by synthesized by adding, at 70°C, glycidol (for example, a product manufactured by Junsei Chemical Co., Ltd.) to an isocyanate oligomer having an IPDI isocyanurate structure (for example, DESMODUR Z4470BA (tradename) manufactured by Bayer) such that the number of NCO groups becomes the same as the number of OH groups, and further adding a tin-based catalyst (for example, NEOSTANN U-100 (tradename) manufactured by Nitto Kasei Co., Ltd.) in an amount of 0.05% by mass.
- glycidol for example, a product manufactured by Junsei Chemical Co., Ltd.
- an isocyanate oligomer having an IPDI isocyanurate structure for example, DESMODUR Z4470BA (tradename) manufactured by Bayer
- a tin-based catalyst for example,
- the polythiol compound (A) it is preferable to use one ring-structure-containing epoxy compound singly, or two or more ring-structure-containing epoxy compounds in combination, as the compound (B) having plural epoxy groups. Among them, it is more preferable to use one bisphenol A skeleton epoxy compound or urethane bond-containing epoxy compound singly, or two or more selected from the group consisting of bisphenol A skeleton epoxy compounds and urethane bond-containing epoxy compounds in combination.
- the term "radical generator” refers to a compound that generates a radical when energy from, for example, light or heat is imparted to the compound.
- the radical generator(s) (C) to be used are thermal radical generators including a peroxide. Such radical generators are used from the viewpoints of improving the adhesive power and enabling the adhesion of a light-nontransmissive rubber.
- Examples of the thermal radical generators including a peroxide include thermal radical generators including an organic peroxide and thermal radical generators including an inorganic peroxide. Thermal radical generators including an organic peroxide are more preferable.
- One radical generator may be used singly as the radical generator (C), or two or more radical generators may be used in combination as the radical generator (C).
- the thermal radical generator(s) including an organic peroxide to be used is, for example, at least one selected from the group consisting of t-butyl peroxy-2-ethylhexanoate, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1,1-di(t-hexylperoxy)cyclohexanone, di-t-butyl peroxide, t-butyl cumyl peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, t-amyl peroxy-2-ethylhexanoate, di(2-t-butylperoxyisopropyl)benzene, di(t-butyl) peroxide, 1,1'-di(2-t-butylperoxyisopropyl)benzene, peroxybenzoyl, 1,1-di(t-
- the thermal radical generator(s) including an organic peroxide is preferably at least one selected from the group consisting of t-butyl peroxy-2-ethylhexanoate, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1,1-di(t-hexylperoxy)cyclohexanone, di-t-butyl peroxide and t-butyl cumyl peroxide.
- One thermal radical generator including an organic peroxide may be used singly, or two or more thermal radical generators each including an organic peroxide may be used in combination.
- the thermal radical generator including an inorganic peroxide is, for example, a redox radical generator composed of a combination of an oxidant and a reductant, such as a combination of a hydrogen peroxide and an iron (II) salt or a combination of a persulfuric acid salt and sodium hydrogen sulfite.
- a redox radical generator composed of a combination of an oxidant and a reductant, such as a combination of a hydrogen peroxide and an iron (II) salt or a combination of a persulfuric acid salt and sodium hydrogen sulfite.
- One thermal radical generator including an inorganic peroxide may be used singly, or two or more thermal radical generators each including an inorganic peroxide may be used in combination.
- amine-based catalyst refers to a catalyst that has an amine skeleton and that contributes to the reaction of abstracting a proton from a thiol group in the polythiol compound (A).
- the reaction of abstracting a proton is an initiation reaction for anionic polymerization between thiol groups and epoxy groups.
- the amine-based catalyst is, for example, a diamine, and specific examples thereof include bis(2-dimethylaminoethyl) ether, N,N,N', N'-tetramethyl hexamethylenediamine, triethylenediamine (TEDA), benzyl dimethyl amine, 2,2'-dimorpholinoethyl ether, and N-methylmorpholine. Among these, triethylenediamine (TEDA) is preferable.
- the catalyst such as those described above, may be used singly, or in combination of two or more thereof.
- composition used in the present invention may further include optional components.
- optional components include urethanization catalysts, surface controllers, solvents, binders, fillers, pigment dispersants, electric conductivity imparting agents, ultraviolet absorbers, antioxidants, anti-drying agents, penetrants, pH adjusters, metal chelating agents, mildewproof agents, antibacterial agents, surfactants, plasticizers, waxes, and leveling agents.
- the composition used in the present invention may further include a surface controller (hereinafter also referred to as "surface controller (E)"), as necessary.
- a surface controller hereinafter also referred to as "surface controller (E)
- Any surface controller may be used as the surface controller (E).
- the surface controller include acrylic surface controllers, vinyl-based surface controllers, silicone-based surface controllers, fluorine-based surface controllers and silicone acrylate-based surface controllers.
- silicone acrylate-based surface controllers are preferable from the viewpoints of compatibility and the ability to decrease surface tension.
- the composition used in the present invention may include a solvent, as necessary.
- the solvent may be any solvent that does not react with other components, without particular limitation. Examples thereof include aromatic solvents and aliphatic solvents.
- aromatic solvents include toluene and xylene.
- aliphatic solvents include hexane, methyl ethyl ketone (MEK), and butyl acetate.
- composition used in the present invention may include a compound that includes a carbon-carbon double bond, as an optional component.
- a high content of the compound that includes a carbon-carbon double bond may make difficult the occurrence of a chemical bonding reaction between a sulfur atom of a thiol group of the polythiol compound (A) and a carbon atom in a carbon-carbon bond due to a hydrogen abstraction reaction from the main chain of the rubber formed by carbon-carbon bonds, and may decrease the adhesive power of the composition with respect to the rubber.
- the ratio of the total molar number of carbon-carbon double bonds contained in the carbon-carbon double bond-containing compound contained in the composition relative to the total molar number of thiol groups contained in the polythiol compound (A) contained in the composition (carbon-carbon double bonds/thiol groups) is lower than 0.4, preferably lower than 0.1, more preferably 0.08 or lower, further more preferably 0.05 or lower, and particularly preferably 0.01 or lower.
- the total molar number of carbon-carbon double bonds contained in the carbon-carbon double bond-containing compound contained in the composition can be obtained by multiplying the molar number of the compound contained in the composition by the number of carbon-carbon double bonds contained in one molecule of the compound.
- the molar ratio (carbon-carbon double bonds/thiol groups) can be obtained by dividing the obtained total molar number of contained carbon-carbon double bonds by the total molar number of thiol groups contained in the polythiol compound (A) contained in the composition.
- the ratio (Ep/SH) of the total molar number (Ep) of epoxy groups contained in the compound (B) having plural epoxy groups to the total molar number (SH) of thiol groups contained in the polythiol compound (A) is 0.50 or higher but lower than 2.00.
- the ratio (Ep/SH) is lower than 0.50, the composition may not harden with sufficient tightness, and the adhesive power may decrease.
- the ratio (Ep/SH) is 2.00 or higher, the amount of thiol groups in the component (A) is small relative to the amount of epoxy groups in the component (B), as a result of which the thiol-ene reaction between thiol groups and carbon-carbon double bonds on the rubber surface may not sufficiently proceed, the composition may not tightly adhere to the rubber, and the interfacial adhesive power may decrease. Therefore, the ratio (Ep/SH) is, for example, from 0.50 to 1.80.
- the ratio (Ep/SH) is preferably 0.60 or higher.
- the ratio (Ep/SH) is preferably 1.5 or lower.
- the ratio (Ep/SH) is more preferably from 0.8 to 1.3.
- the total molar number (SH) of thiol groups contained in the polythiol compound (A) can be obtained by multiplying the molar number of the polythiol compound (A) by the number of thiol groups contained in one molecule of the polythiol compound (A).
- the total molar number (SH) of thiol groups contained in the polythiol compound (A) refers to the total amount of thiol groups contained in the total amount of polythiol compound (A) contained in the composition according to the present invention, and does not refer to the number of thiol groups contained in one molecule of the polythiol compound.
- the total molar number (Ep) of epoxy groups contained in the compound (B) having plural epoxy groups can be obtained by dividing the weight content of the compound (B) having plural epoxy groups by the theoretical molecular weight thereof, and multiplying the obtained value by the number of epoxy groups contained in one molecule of the compound (B) having plural epoxy groups.
- the total molar number (Ep) of epoxy groups contained in the compound (B) having plural epoxy groups refers to the total amount of epoxy groups contained in the total amount of compound (B) having plural epoxy groups contained in the composition according to the present invention, and does not refer to the number of epoxy groups contained in one molecule of the compound having plural epoxy groups.
- the number of epoxy groups contained in one molecule of the component (B) can be calculated using the following method.
- the epoxy equivalent weight of the epoxy resin (the mass of the resin that includes one equivalent of epoxy groups) is measured using the method according to JIS K7236:2001.
- the number average molecular weight of the epoxy resin is divided by the obtained epoxy equivalent weight to calculate the number of epoxy groups contained in one molecule of the component (B).
- the number average molecular weight refers to a styrene-equivalent number average molecular weight.
- the number average molecular weight of the epoxy resin can be obtained using a chromatographic method.
- the molecular structures and the contents of the component (A) and the component (B) contained in the composition may be determined using known measurement methods, such as an NMR measurement or an IR measurement, and then the values of SH and Ep may be obtained using the method described above.
- the ratio of the total molar number of the radical generator (C) contained in the composition to the total molar number of thiol groups contained in the polythiol compound (A) is preferably 0.025 or higher.
- the ratio is preferably 0.03 or higher, more preferably 0.035 or higher, and particularly preferably 0.04 or higher.
- the ratio (radical generator (C)/thiol groups) is preferably 0.5 or lower, more preferably 0.45 or lower, and particularly preferably 0.4 or lower.
- the content of the amine-based catalyst (D) in the composition used in the present invention is preferably 0.005 parts by mass to 5 parts by mass, more preferably from 0.01 parts by mass to 4 parts by mass, and particularly preferably from 0.05 parts by mass to 3.5 parts by mass, relative to 100 parts of the polythiol compound (A), from the viewpoint of increasing the film strength and the adhesive power by sufficiently promoting the reaction between the polyol compound (A) and the compound (B) having plural epoxy groups.
- the composition used in the present invention may include optional components (for example, the surface controlling agent (E), the compound that includes a carbon-carbon double bond, or the solvent) in addition to the components (A) to (D).
- the total content of the components (A) to (D), excluding solvents, in the composition is preferably 80% by mass or higher, more preferably 90% by mass or higher, still more preferably 95% by mass or higher, and further preferably 98% by mass or higher, with respect to the total amount, excluding solvents, of the composition.
- the total content of the components (A) to (E), excluding solvents, in the composition is preferably 90% by mass or higher, more preferably 95% by mass or higher, still more preferably 99% by mass or higher, and further preferably 100% by mass, with respect to the total amount, excluding solvents, of the composition.
- the composition used in the present invention is able to exhibit high adhesive power to rubber.
- the composition used in the present invention can suitably be used, as a composition for adhesion, in an adhesive particularly suitable for application to rubber or in a layered body that includes a rubber layer and an adhesion layer, as described below.
- the applications of the composition according to the present invention are not limited thereto; for example, colored particles may be incorporated into the composition used in the present invention, in which case the composition may be used as a coating material for imparting decoration.
- the adhesive used in the present invention includes the composition used in the present invention.
- the adhesive may include components other than the composition used in the present invention, so long as the effect of the present invention is not hindered.
- the content of the composition in the adhesive is preferably 90% by mass or higher, more preferably 95% by mass or higher, still more preferably 99% by mass or higher, and further preferably 100% by mass, with respect to the total amount, excluding solvents, of the adhesive.
- the layered body according to the present invention includes, in the recited order, a rubber layer, an adhesion layer formed using the composition according to the present invention, and another layer.
- the layered body according to the present invention is a layered body (laminated body) which includes plural layers adhered to one another, and in which at least one of the layers is a rubber layer, and in which the rubber layer is adhered to an adjacent layer via an adhesion layer formed using the composition or the adhesive
- the rubber layer and the other layer are not particularly limited except that they should have an adhesion face with which the adhesion layer contacts; the adhesion face is not limited to a flat plane, and may be a curved face or a face having irregularities.
- the entire adhesion face of the rubber layer and/or the entire adhesion face of the other layer may be adhered via the adhesion layer, or only a part of the adhesion face of the rubber layer and/or only a part of the adhesion face of the other layer may be adhered via the adhesion layer.
- the layered body according to the present invention may have a configuration in which three or more layers, including a rubber layer, are layered with the adhesion layer(s) according to the present invention disposed therebetween. This configuration is not limited to a configuration in which all of the layers are adhered to one another via the adhesion layer according to the present invention.
- Each of the other layers may be a rubber layer, or a layer other than a rubber layer, such as a glass layer, a metal layer or a resin layer.
- each layer and the number of layers may be selected, as appropriate, in accordance with the purpose.
- the rubber layer may be formed from vulcanized rubber or unvulcanized rubber.
- the rubber constituting the rubber layer preferably has a carbon-carbon double bond.
- a carbon atom of a carbon-carbon double bond contained in the rubber layer contacting the adhesion layer forms a carbon-sulfur bond with a sulfur atom of a thiol group of the polythiol compound (A) contained in the composition according to the present invention.
- a layered body can be obtained even when the rubber constituting the rubber layer does not have a carbon-carbon double bond.
- a sulfur atom of a thiol group of the polythiol compound (A) and a carbon atom of a carbon-carbon bond chemically binds to each other via a hydrogen abstraction reaction in which the polythiol compound (A) pulls out hydrogen from the main chain formed by carbon-carbon bonds present in the rubber.
- the rubber constituting the rubber layer has a carbon-carbon double bond.
- the material of the rubber layer is not particularly limited, and examples thereof include: natural rubber (NR); conjugated diene synthetic rubber, such as polyisoprene synthetic rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), and butyl rubber (IIR); ethylene-propylene copolymer rubber (EPM); ethylene-propylene-diene copolymer rubber (EPDM); and polysiloxane rubber.
- NR natural rubber
- conjugated diene synthetic rubber such as polyisoprene synthetic rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), and butyl rubber (IIR)
- EPM ethylene-propylene copolymer rubber
- EPDM
- Examples of the other layers than the rubber layer include a glass layer, a metal layer, and a resin layer. Strong adhesion of a metal layer or a resin layer to the rubber layer can be achieved by using the composition according to the present invention.
- the adhesive is applied to an adhesion face of a rubber layer. Then, after being left to stand for a predetermined period of time, if necessary, an adhesion face of another layer that should face the rubber layer is brought into contact with the face to which the adhesive has been applied (the adhesion face of the rubber layer), to obtain a layered body.
- the adhesive may have been applied also to the adhesion face of the other layer that should face the rubber layer.
- the adhesive may be applied to an adhesion face of another layer that should face a rubber layer. Then, after being left to stand for a predetermined period of time, if necessary, an adhesion face of the rubber layer is brought into contact with the face to which the adhesive has been applied (the adhesion face of the other layer), to obtain a layered body. In this process, the adhesive may have also been applied to the adhesion face of the rubber layer.
- the period during which the face is left to stand is preferably from 0 to 30 minutes, and more preferably from 1 to 15 minutes, from the viewpoint of maintaining the shape of the adhesive such that the adhesive would not exude from the layered body at the time of curing.
- the pressure is preferably from 0 to 5 MPa, more preferably from 0 to 2.5MPa, and particularly preferably from 0 to 1 MPa, from the viewpoint of improving the adhesive power and preventing or suppressing exudation of the adhesive from the layered body.
- the pressing time is preferably from 5 to 120 minutes, more preferably from 10 to 60 minutes, and particularly preferably from 15 to 45 minutes.
- the curing of the adhesive is preferably performed by heating.
- a temperature at which the thermal radical generator generates radicals efficiently may appropriately be selected as the heating temperature, and the heating temperature is preferably a temperature that is within about ⁇ 30°C from the temperature at which the half-life of the thermal radical generator is one minute.
- the curing is preferably performed by photoirradiation.
- a ultraviolet (UV) lamp is preferably used as the light source from the viewpoints of improving the adhesive power and reducing costs.
- the photoirradiation time is preferably from several seconds to several tens of seconds.
- PMP Pentaerythritol tetrakis(3-mercaptopropionate)
- Cresol-novolac-type epoxy compound JER152 (tradename) manufactured by Mitsubishi Chemical Corporation Bisphenol A-type Epoxy Compound: EP-4100 (tradename) manufactured by ADEKA CORPORATION Hydrogenated bisphenol A-type epoxy compound: EPOLIGHT4000 (tradename) manufactured by KYOEISHA CHEMICAL Co., Ltd.
- EPOLIGHT4000 Japanese Organic Chemical Vapor Company
- PERBUTYL O (tradename) manufactured by NOF CORPORATION
- Silicone acrylate-based surface controller SIU2400 (tradename) manufactured by Toyo Chemicals Co., Ltd.
- the total molar number (SH) of thiol groups contained in the polythiol compound (A) was calculated by dividing the addition amount by the theoretical molecular weight, and multiplying the obtained value by the number of thiol groups contained in one molecule of the polythiol compound (A).
- the total molar number (Ep) of epoxy groups contained in JER152 as the component (B) was obtained by calculation based on the method according to JIS K7236:2001.
- the total molar number (Ep) of epoxy groups was obtained by dividing the addition amount mentioned above by the theoretical molecular weight, and multiplying the obtained value by the number of epoxy groups contained in one molecule of the component (B).
- Rubber having a length of 100 mm, a width of 25 mm, and a thickness of 3 mm was produced from the formulation indicated in the following Table 1.
- Table 1 Type of Rubber NR/SBR NR Formulation NR 15 100 SBR 85 - Carbon Black 50 50 Stearic Acid 2 2 Anti-aging Agent 1 1 Zinc Oxide 3 3 Vulcanization Accelerator 1 0.4 0.4 Vulcanization Accelerator 2 0.2 0.2 Sulfur 1.4 1.4 *Numbers in the table indicate parts by mass
- the obtained adhesive was applied, in a thickness of 30 ⁇ m, to two rubber sheets (rubber substrates), and the coated faces were adhered to each other and curing was performed, as a result of which a layered body was prepared.
- the curing was performed by maintaining the adhered bodies at a temperature of 150°C while applying a pressure of 0.05 MPa for 20 minutes. Then, the adhesive power of the cured body of the adhesive (the adhesion layer) was measured as described below. The results thereof (evaluation results) are indicated in Table 2.
- the opposite ends of the adjacent rubber substrates in the layered body were pulled away from each other (in the directions normal to the principal faces of the rubber substrates, the directions forming an angle of 180°) at a pulling rate of 50 mm/min., and the delamination strength (N/25mm) was measured and used as an indicator of the adhesive power.
- a delamination strength of 100N/25mm or greater indicates that a sufficient adhesive power at a level at which the rubber substrate breaks before delamination occurs is obtained.
- the delamination strength is preferably 300N/25mm or greater.
- a delamination strength of less than 100N/25mm indicates that the reaction at the interface between the rubber substrate and the adhesive has not proceeded sufficiently, and delamination would occur at the interface or the adhesive itself would undergo cohesive failure due to insufficient cohesive force of the adhesive. Occurrence of such a phenomenon indicates that the adhesive power is insufficient.
- the adhesive power in Examples 1 to 14 was high due to the inclusion of the components (A) to (D), and the ratio (Ep/SH) of the total molar number of epoxy groups contained in the component (B) to the total molar number of thiol groups contained in the component (A) being from 0.50 to less than 2.00.
- composition according to the present invention can suitably be used in an adhesive suitable for, particularly, application to rubber, and in a layered body including a rubber layer and an adhesion layer.
- applications of the composition according to the present invention are not limited thereto, and the composition can also be used, for example, as a coating material to which colored particles are incorporated, and which is used for imparting decoration.
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Description
- The present invention relates to a composition, an adhesive and a layered body, and more specifically relates to a composition and an adhesive that are suitable for adhesion to rubber, and a layered body in which a rubber layer is adhered using the composition.
- Although materials exhibiting excellent adhesive power to vulcanized rubber have thus far been desired, there has not been a material which provides sufficient adhesive power to vulcanized rubber. Methods employed for adhering vulcanized rubber are disclosed, for example, in Japanese Patent Application Laid-open (
JP-A) No. HI0-139901 JP-A No. H10-139901 JP2001-131262 - The method described in
JP-A No. H10-139901 - In consideration of the above circumstances, an object of the present invention is to provide a composition capable of exhibiting high adhesive power to rubber, and a layered body in which a rubber layer and an adhesion layer formed using the composition are adhered.
- In order to achieve the above object, according to an aspect of the present invention, a a layered body is provided according to claim 1.
- According to another aspect of the present invention, an adhesive that includes the above-described composition is provided. According to still another aspect of the invention, a layered body is provided which includes, in this order, a rubber layer, an adhesion layer formed using the composition of any one of [1] to [3], and another layer.
- According to the present invention, it is possible to provide a composition capable of exhibiting high adhesive power to rubber, and a layered body in which a rubber layer and an adhesion layer formed using the composition are adhered.
- The composition used in the present invention is a composition as in claim 1.
- The composition used in the present invention is able to exhibit a high adhesive power to rubber. Further, the composition used in the present invention is able to exhibit a high adhesive power to vulcanized rubber as well as to unvulcanized rubber. Although the reason therefor is not clear, it is presumed that the following may be the reason.
- First, it is conceivable that the composition used in the present invention strongly hardens through an anionic polymerization reaction between a part of the amount of the polythiol compound (A) and the compound (B) having plural epoxy groups. An adhesion layer formed using the composition used in the present invention thereby may acquire sufficient film strength, conceivably due to the strong hardening.
- Another part of polythiol compound (A) becomes a thiyl radical as a result of the radical generator (C) that has been activated by energy, such as heat or light. It is conceivable that the so-formed thiyl radical reacts with a carbon-carbon double bond present in rubber. The composition used in the present invention exhibits high interfacial adhesive power to rubber, conceivably because the composition according to the present invention chemically binds to rubber through the thiol-ene reactions as described above. In particular, the composition used in the present invention exhibits high interfacial adhesive power to vulcanized rubber as well as to unvulcanized rubber, conceivably because carbon-carbon double bonds are present not only in unvulcanized rubber but also in vulcanized rubber.
- As described above, an adhesion layer having both high interfacial adhesive power to rubber and high film strength can be formed using the composition used in the present invention. Therefore, when a composition used in the present invention is used as an adhesive, high adhesive power to an adherend (particularly, rubber) can be exhibited.
- It is also conceivable that chemical bonding between a sulfur atom in a thiol group in the polythiol compound (A) and a carbon atom in a carbon-carbon bond occurs as a result of a hydrogen abstraction reaction from the main chain formed by carbon-carbon bonds present in the rubber. Therefore, the composition used in the present invention is able to exhibit adhesive power to rubber even when carbon-carbon double bonds are not necessarily present in the rubber.
- Use of the composition enables sufficiently high adhesive power to be exhibited with respect to rubbers in general, even in the case where surface roughening treatment, such as grinding, is not carried out on the surfaces of the adhesion faces of the rubbers, conceivably because the composition and the rubber chemically bind to each other as described above. Omitting a surface roughening treatment on the adhesion face of the rubber, as described above, provides for simplification and improved efficiency of an adhesion process. Nevertheless, it is acceptable to carry out surface roughening treatment on the adhesion face of the rubber when using the composition In particular, when using a liquid-form or paste-form adhesive that includes the composition used in the present invention, surface roughening treatment may be carried out on the surface on the adhesion face of the rubber, thereby improving the adhesive power via the utilization of an anchor effect.
- Since the composition used in the present invention is able to exhibit high adhesive power to vulcanized rubber, adhesion can be achieved at a remarkably lower temperature and over a remarkably shorter length of time (for example, from 100 to 150°C for from 3 to 30 minutes) than when unvulcanized rubber materials are brought into contact with each other and adhesion is performed while vulcanizing them.
- In the present specification, the polythiol compound (A), the compound (B) having plural epoxy groups, the radical generator (C), the amine-based catalyst (D), and the after-mentioned surface adjustor (E) are also referred to as "component (A)", "component (B)", "component (C)", "component (D)", and "component (E)", respectively, in some cases.
- In the present invention, the term "polythiol compound" refers to a compound having two or more thiol groups in one molecule thereof. As the component (A), one polythiol compound may be used singly, or two or more polythiol compounds may be used in combination.
- In the polythiol compound (A), the number of thiol groups in one molecule thereof is not particularly limited as long as the above-defined relationship with the total molar number of epoxy groups in the component (B) is satisfied. From the viewpoint of improving the adhesive power, the polythiol compound (A) preferably has three or more thiol groups in one molecule thereof. The upper limit of the number of thiol groups in one molecule of the polythiol compound (A) is not particularly limited, and may be selected, as appropriate, as long as the effects according to the present invention are not impaired. The number of thiol groups in one molecule of the polythiol compound (A) may be appropriately selected within the range of usually from 2 to 7, preferably from 3 to 6, and more preferably from 3 to 4, although the number may vary depending on whether the polythiol compound (A) is a low-molecular-weight compound or a high-molecular-weight compound. However, these ranges should not be construed as limiting the scope of the present invention.
- The scope of the polythiol compound (A) encompasses primary thiols, secondary thiols, and tertiary thiols. Primary thiols are preferable from the viewpoint of improving the adhesive power.
- The molecular weight of the polythiol compound (A) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, further more preferably 900 or less, and particularly preferably 800 or less, from the viewpoint of improving the adhesive power. Further, the lower limit of the molecular weight of the polythiol compound (A) is not particularly limited. The lower limit of the molecular weight of the polythiol compound (A) is preferably 200 or more, and still more preferably 300 or more. When the polythiol compound (A) is a polymer, the "molecular weight" refers to the styrene-equivalent number average molecular weight.
- Examples of the polythiol compound (A) include an aliphatic polythiol that may include a heteroatom and an aromatic polythiol that may include a heteroatom. An aliphatic polythiol that may include a heteroatom is preferable from the viewpoint of improving the adhesive power.
- The "aliphatic polythiol that may include a heteroatom" refers to an aliphatic compound that has two or more thiol groups in one molecule thereof and that may include a heteroatom. The "aromatic polythiol that may include a heteroatom" refers to an aromatic compound that has two or more thiol groups in one molecule thereof and that may include a heteroatom.
- From the viewpoint of improving the adhesive power, the included heteroatom, or heteroatoms, is preferably at least one kind selected from the group consisting of oxygen, nitrogen, sulfur, phosphorus, halogen, and silicon; is more preferably at least one kind selected from the group consisting of oxygen, nitrogen, sulfur, phosphorus, and halogen; and is particularly preferably at least one kind selected from the group consisting of oxygen, nitrogen, and sulfur.
- Examples of the aliphatic polythiol that may include a heteroatom include: a polythiol in which the portion other than the thiol groups is an aliphatic hydrocarbon, such as an alkanedithiol having from 2 to 20 carbon atoms; a polythiol obtainable by replacing halogen atoms of a halohydrin adduct of an alcohol by thiol groups; a polythiol that is a hydrogen sulfide reaction product of a polyepoxide compound; a thioglycolic acid ester obtainable by an ester-forming reaction between a polyhydric alcohol having from 2 to 6 hydroxyl groups in a molecule thereof and thioglycolic acid; a mercapto fatty acid ester obtainable by an ester-forming reaction between a polyhydric alcohol having from 2 to 6 hydroxyl groups in a molecule thereof and a mercapto fatty acid; a thiol isocyanurate compound obtainable by a reaction between an isocyanurate compound and a thiol; a thiol that includes a polysulfide group; a silicone modified with thiol groups; and silsesquioxane modified with thiol groups.
- Examples of the polyhydric alcohol having from 2 to 6 hydroxyl groups in a molecule thereof include an alkanediol having from 2 to 20 carbon atoms, a poly(oxyalkylene)glycol, glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.
- Among the above-exemplified aliphatic polythiols that may include a heteroatom, from the viewpoint of improving the adhesive power, a polythiol in which the portion other than the thiol groups is an aliphatic hydrocarbon, a polythiol obtainable by replacing halogen atoms of a halohydrin adduct of an alcohol by thiol groups, a polythiol that is a hydrogen sulfide reaction product of a polyepoxide compound, a thioglycolic acid ester, a mercapto fatty acid ester, and a thiol isocyanurate compound are preferable; a mercapto fatty acid ester and a thiol isocyanurate compound are more preferable; and a mercapto fatty acid ester is particularly preferable. From similar viewpoints, a thiol that does not include a polysulfide group or a siloxane bond is also preferable.
- The polythiol in which the portion other than thiol groups is an aliphatic hydrocarbon is, for example, an alkanedithiol having from 2 to 20 carbon atoms.
- Examples of the alkanedithiol having from 2 to 20 carbon atoms include 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 1-1-cyclohexanedithiol, and 1,2-cyclohexanedithiol.
- Examples of the thioglycolic acid ester include 1,4-butanediol bisthioglycolate, 1,6-hexanediol bisthioglycolate, trimethylolpropane tristhioglycolate, and pentaerythritol tetrakisthioglycolate.
- The mercapto fatty acid ester is preferably a β-mercapto fatty acid ester having a primary thiol group, and is more preferably a β-mercaptopropionic acid ester of a polyhydric alcohol having from 2 to 6 hydroxyl groups in a molecule thereof, from the viewpoint of improving the adhesive power. Further, the mercapto fatty acid ester having a primary thiol group preferably has from 4 to 6 thiol groups in one molecule thereof, more preferably has 4 or 5 thiol groups in one molecule thereof, and further preferably has 4 thiol groups in one molecule thereof, from the viewpoint of improving the adhesive power.
- Preferable examples of the β-mercaptopropionic acid ester having a primary thiol group include tetraethyleneglycol bis(3-mercaptopropionate) (EGMP-4), trimethylolpropane tris(3-mercaptopropionate) (TMMP), pentaerythritol tetrakis(3-mercaptopropionate) (PEMP), and dipentaerythritol hexakis(3-mercaptopropionate) (DPMP). Among these, PEMP and DPMP are preferable, and PEMP is more preferable.
- The β-mercaptopropionic acid ester having a secondary thiol group is, for example, an ester between a polyhydric alcohol having from 2 to 6 hydroxyl groups in a molecule thereof and β-mercaptobutanoic acid, and specific examples thereof include 1,4-bis(3-mercaptobutylyloxy)butane and pentaerythritol tetrakis(3-mercaptobutyrate).
- The thiol isocyanurate compound, which is obtainable via a reaction between an isocyanurate compound and a thiol, is preferably a thiol isocyanurate compound having a primary thiol group, from the viewpoint of improving the adhesive power. Further, the thiol isocyanurate compound having a primary thiol group preferably has 2 to 4 thiol groups in one molecule thereof, and more preferably has 3 thiol groups in one molecule thereof, from the viewpoint of improving the adhesive power.
- The thiol isocynaurate compound having a primary thiol group is preferably tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (TEMPIC).
- Examples of the silicone modified with thiol groups include mercapto-modified silicone oils such as KF-2001, KF-2004, and X-22-167B (tradenames, manufactured by Shin-etsu Chemical Co., Ltd.), SMS042 and SMS022 (tradenames, manufactured by Gelest Inc.), and PS849 and PS850 (tradenames, manufactured by UCT Inc.).
- Examples of aromatic polythiols that may be used as the polythiol compound (A) include the aromatic polythiols exemplified below. As described above, the aromatic polythiol may include a heteroatom. Specifically, examples of the aromatic polythiols include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, and 2,4-di(p-mercaptophenyl)pentane.
- In the present invention, the term "compound having plural epoxy groups" refers to a compound having two or more epoxy groups in one molecule thereof. As the component (B), one compound having plural epoxy groups may be used singly, or two or more compounds each having plural epoxy groups may be used in combination.
- In the component (B), the number of epoxy groups in one molecule thereof is not particularly limited, as long as the above-defined relationship with the total molar number of thiol groups of the component (A) is satisfied. From the viewpoint of improving the adhesive properties and the durability of adhesion, the number of epoxy groups in one molecule of the component (B) may be determined, as appropriate, within a range of usually 2 or more, although the number may vary depending on whether the component (B) is a low-molecular-weight compound or a high-molecular-weight compound.
- The epoxy equivalent weight of the compound (B) having plural epoxy groups is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, further more preferably 900 or less, and particularly preferably 800 or less, from the viewpoint of improving the adhesive properties. The lower limit of the molecular weight of the component (B) is not particularly limited, and is preferably, for example, 50 or more, and more preferably 100 or more. When component (B) is a polymer, the "molecular weight" refers to the styrene-equivalent number average molecular weight.
- Examples of the compound (B) having plural epoxy groups include an aromatic epoxide, an aliphatic epoxide, an alicyclic epoxide, and modified products thereof. Among these, an aromatic epoxide having a ring structure other than a glycidyl group, an alicyclic epoxide having a ring structure other than a glycidyl group, and modified products thereof are preferable. From the viewpoint of improving the adhesive power of the adhesion layer, the aromatic epoxide preferably has two or more aromatic rings. The alicyclic epoxide preferably has three or more aliphatic rings.
- Examples of the aromatic epoxide include: bisphenol-type aromatic epoxides such as a bisphenol A-type epoxy compound, a bisphenol F-type epoxy compound, and a bisphenol S-type epoxy compound; novolac resin-type aromatic epoxides such as a phenol novolac-type epoxy compound and a cresol novolac-type epoxy compound; and other aromatic epoxides such as a polyphenol-type epoxy compound, a biphenyl-type epoxy compound, a naphthalene ring-containing epoxy compound, and a fluorene-type epoxy compound. The aromatic epoxide may have a urethane skeleton.
- Examples of the aliphatic epoxide include a polyalkyleneglycol diglycidyl ether such as trimethylolpropane triglycidyl ether, and a polyglycidyl ether of a polyhydric alcohol such as glycerin.
- The alicyclic epoxide is, for example, an alicyclic epoxide such as cyclohexane dimethanol diglycidyl ether. The alicyclic epoxide may have a urethane skeleton.
- Modified products of the aromatic, aliphatic or alicyclic epoxide include modified products of aromatic epoxides such as a hydrogenated bisphenol A-type epoxy compound, a hydrogenated bisphenol F-type epoxy compound, a hydorgenated biphenyl-type epoxy compound, and a brominated bisphenol-type epoxy compound.
- Among them, a cresol novolac-type epoxy compound (for example, JER152 (tradename, manufactured by Mitsubishi Chemical Corporation), which is the following epoxy compound B-1), a bisphenol A-type epoxy compound (for example JER1001B80 (tradename, manufactured by Mitsubishi Chemical Corporation), which is the following epoxy compound B-2, or EP-4100 (tradename, manufactured by ADEKA Corporation), which is the following epoxy compound B-3), an aromatic epoxide having a urethane skeleton (for example, the following epoxy compound B-4), an alicyclic epoxide having a urethane skeleton (for example, the following epoxy compound B-5), and a hydrogenated bisphenol A-type epoxy compound (for example, EPOLIGHT4000 (tradename, manufactured by KYOEISHA CHEMICAL Co., Ltd.), which is the following epoxy compound B-6) are preferable.
- Here, epoxy compound B-4 illustrated above can be synthesized in the following manner. Specifically, epoxy compound B-4 can be synthesized by adding, at 70°C, glycidol (for example, a product manufactured by Junsei Chemical Co., Ltd.) to an isocyanate oligomer having a TDI adduct structure (for example, DESMODUR L-75 (tradename) manufactured by Bayer) such that the number of NCO groups becomes the same as the number of OH groups, and further adding a tin-based catalyst (for example, NEOSTANN U-100 (tradename) manufactured by Nitto Kasei Co., Ltd.) in an amount of 0.05% by mass.
- Here, epoxy compound B-5 illustrated above can be synthesized in the following manner. Specifically, epoxy compound B-5 can by synthesized by adding, at 70°C, glycidol (for example, a product manufactured by Junsei Chemical Co., Ltd.) to an isocyanate oligomer having an IPDI isocyanurate structure (for example, DESMODUR Z4470BA (tradename) manufactured by Bayer) such that the number of NCO groups becomes the same as the number of OH groups, and further adding a tin-based catalyst (for example, NEOSTANN U-100 (tradename) manufactured by Nitto Kasei Co., Ltd.) in an amount of 0.05% by mass.
- In the case of using a mercapto fatty acid ester and a thiol isocyanurate compound as the polythiol compound (A), it is preferable to use one ring-structure-containing epoxy compound singly, or two or more ring-structure-containing epoxy compounds in combination, as the compound (B) having plural epoxy groups. Among them, it is more preferable to use one bisphenol A skeleton epoxy compound or urethane bond-containing epoxy compound singly, or two or more selected from the group consisting of bisphenol A skeleton epoxy compounds and urethane bond-containing epoxy compounds in combination.
- The term "radical generator" refers to a compound that generates a radical when energy from, for example, light or heat is imparted to the compound. The radical generator(s) (C) to be used are thermal radical generators including a peroxide. Such radical generators are used from the viewpoints of improving the adhesive power and enabling the adhesion of a light-nontransmissive rubber. Examples of the thermal radical generators including a peroxide include thermal radical generators including an organic peroxide and thermal radical generators including an inorganic peroxide. Thermal radical generators including an organic peroxide are more preferable.
- One radical generator may be used singly as the radical generator (C), or two or more radical generators may be used in combination as the radical generator (C).
- The thermal radical generator(s) including an organic peroxide to be used is, for example, at least one selected from the group consisting of t-butyl peroxy-2-ethylhexanoate, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1,1-di(t-hexylperoxy)cyclohexanone, di-t-butyl peroxide, t-butyl cumyl peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, t-amyl peroxy-2-ethylhexanoate, di(2-t-butylperoxyisopropyl)benzene, di(t-butyl) peroxide, 1,1'-di(2-t-butylperoxyisopropyl)benzene, peroxybenzoyl, 1,1-di(t-butylperoxy)cyclohexane, di(3,5,5-trimethylhexanoyl)peroxide, t-butyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, and dicumyl peroxide. Among these, the thermal radical generator(s) including an organic peroxide is preferably at least one selected from the group consisting of t-butyl peroxy-2-ethylhexanoate, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1,1-di(t-hexylperoxy)cyclohexanone, di-t-butyl peroxide and t-butyl cumyl peroxide. One thermal radical generator including an organic peroxide may be used singly, or two or more thermal radical generators each including an organic peroxide may be used in combination.
- The thermal radical generator including an inorganic peroxide is, for example, a redox radical generator composed of a combination of an oxidant and a reductant, such as a combination of a hydrogen peroxide and an iron (II) salt or a combination of a persulfuric acid salt and sodium hydrogen sulfite. One thermal radical generator including an inorganic peroxide may be used singly, or two or more thermal radical generators each including an inorganic peroxide may be used in combination.
- In the present invention, the term "amine-based catalyst" refers to a catalyst that has an amine skeleton and that contributes to the reaction of abstracting a proton from a thiol group in the polythiol compound (A). The reaction of abstracting a proton is an initiation reaction for anionic polymerization between thiol groups and epoxy groups.
- The amine-based catalyst is, for example, a diamine, and specific examples thereof include bis(2-dimethylaminoethyl) ether, N,N,N', N'-tetramethyl hexamethylenediamine, triethylenediamine (TEDA), benzyl dimethyl amine, 2,2'-dimorpholinoethyl ether, and N-methylmorpholine. Among these, triethylenediamine (TEDA) is preferable. The catalyst, such as those described above, may be used singly, or in combination of two or more thereof.
- The composition used in the present invention may further include optional components. Examples of optional components include urethanization catalysts, surface controllers, solvents, binders, fillers, pigment dispersants, electric conductivity imparting agents, ultraviolet absorbers, antioxidants, anti-drying agents, penetrants, pH adjusters, metal chelating agents, mildewproof agents, antibacterial agents, surfactants, plasticizers, waxes, and leveling agents.
- The composition used in the present invention may further include a surface controller (hereinafter also referred to as "surface controller (E)"), as necessary. Any surface controller may be used as the surface controller (E). Examples of the surface controller include acrylic surface controllers, vinyl-based surface controllers, silicone-based surface controllers, fluorine-based surface controllers and silicone acrylate-based surface controllers. Among these, silicone acrylate-based surface controllers are preferable from the viewpoints of compatibility and the ability to decrease surface tension.
- The composition used in the present invention may include a solvent, as necessary. The solvent may be any solvent that does not react with other components, without particular limitation. Examples thereof include aromatic solvents and aliphatic solvents.
- Specific examples of the aromatic solvents include toluene and xylene. Examples of the aliphatic solvents include hexane, methyl ethyl ketone (MEK), and butyl acetate.
- The composition used in the present invention may include a compound that includes a carbon-carbon double bond, as an optional component.
- However, a high content of the compound that includes a carbon-carbon double bond results in a reaction between the polythiol compound (A) and the compound that includes a carbon-carbon double bond. This reaction makes it difficult for the polythiol compound (A) and a carbon-carbon double bond in the rubber to undergo a thiol-ene reaction in some cases, and may decrease the adhesive power of the composition with respect to the rubber. Or, a high content of the compound that includes a carbon-carbon double bond may make difficult the occurrence of a chemical bonding reaction between a sulfur atom of a thiol group of the polythiol compound (A) and a carbon atom in a carbon-carbon bond due to a hydrogen abstraction reaction from the main chain of the rubber formed by carbon-carbon bonds, and may decrease the adhesive power of the composition with respect to the rubber. Therefore, the ratio of the total molar number of carbon-carbon double bonds contained in the carbon-carbon double bond-containing compound contained in the composition relative to the total molar number of thiol groups contained in the polythiol compound (A) contained in the composition (carbon-carbon double bonds/thiol groups) is lower than 0.4, preferably lower than 0.1, more preferably 0.08 or lower, further more preferably 0.05 or lower, and particularly preferably 0.01 or lower.
- Here, the total molar number of carbon-carbon double bonds contained in the carbon-carbon double bond-containing compound contained in the composition can be obtained by multiplying the molar number of the compound contained in the composition by the number of carbon-carbon double bonds contained in one molecule of the compound.
- The molar ratio (carbon-carbon double bonds/thiol groups) can be obtained by dividing the obtained total molar number of contained carbon-carbon double bonds by the total molar number of thiol groups contained in the polythiol compound (A) contained in the composition.
- The ratio (Ep/SH) of the total molar number (Ep) of epoxy groups contained in the compound (B) having plural epoxy groups to the total molar number (SH) of thiol groups contained in the polythiol compound (A) is 0.50 or higher but lower than 2.00. When the ratio (Ep/SH) is lower than 0.50, the composition may not harden with sufficient tightness, and the adhesive power may decrease. When the ratio (Ep/SH) is 2.00 or higher, the amount of thiol groups in the component (A) is small relative to the amount of epoxy groups in the component (B), as a result of which the thiol-ene reaction between thiol groups and carbon-carbon double bonds on the rubber surface may not sufficiently proceed, the composition may not tightly adhere to the rubber, and the interfacial adhesive power may decrease. Therefore, the ratio (Ep/SH) is, for example, from 0.50 to 1.80. The ratio (Ep/SH) is preferably 0.60 or higher. The ratio (Ep/SH) is preferably 1.5 or lower. The ratio (Ep/SH) is more preferably from 0.8 to 1.3.
- The total molar number (SH) of thiol groups contained in the polythiol compound (A) can be obtained by multiplying the molar number of the polythiol compound (A) by the number of thiol groups contained in one molecule of the polythiol compound (A). In other words, the total molar number (SH) of thiol groups contained in the polythiol compound (A) refers to the total amount of thiol groups contained in the total amount of polythiol compound (A) contained in the composition according to the present invention, and does not refer to the number of thiol groups contained in one molecule of the polythiol compound.
- Further, the total molar number (Ep) of epoxy groups contained in the compound (B) having plural epoxy groups can be obtained by dividing the weight content of the compound (B) having plural epoxy groups by the theoretical molecular weight thereof, and multiplying the obtained value by the number of epoxy groups contained in one molecule of the compound (B) having plural epoxy groups. In other words, the total molar number (Ep) of epoxy groups contained in the compound (B) having plural epoxy groups refers to the total amount of epoxy groups contained in the total amount of compound (B) having plural epoxy groups contained in the composition according to the present invention, and does not refer to the number of epoxy groups contained in one molecule of the compound having plural epoxy groups.
- When it is difficult to calculate the theoretical molecular weight of the compound (B) having plural epoxy groups (for example, when the component (B) is a polymer (epoxy resin) and the molecular weight of the component (B) is represented by a frequency distribution), the number of epoxy groups contained in one molecule of the component (B) can be calculated using the following method.
- Specifically, the epoxy equivalent weight of the epoxy resin (the mass of the resin that includes one equivalent of epoxy groups) is measured using the method according to JIS K7236:2001. The number average molecular weight of the epoxy resin is divided by the obtained epoxy equivalent weight to calculate the number of epoxy groups contained in one molecule of the component (B). Here, the number average molecular weight refers to a styrene-equivalent number average molecular weight. The number average molecular weight of the epoxy resin can be obtained using a chromatographic method.
- When the total molar number (SH) of thiol groups or the total molar number (Ep) of epoxy groups is obtained after the composition has been prepared or after the adhesion layer has been formed, the molecular structures and the contents of the component (A) and the component (B) contained in the composition (the composition before it forms an adhesion layer) may be determined using known measurement methods, such as an NMR measurement or an IR measurement, and then the values of SH and Ep may be obtained using the method described above.
- The ratio of the total molar number of the radical generator (C) contained in the composition to the total molar number of thiol groups contained in the polythiol compound (A) (radical generator (C)/thiol groups) is preferably 0.025 or higher. When the ratio is 0.025 or higher, the composition is able to exhibit sufficient adhesive power. From the same viewpoint, the ratio (radical generator (C)/thiol groups) is preferably 0.03 or higher, more preferably 0.035 or higher, and particularly preferably 0.04 or higher. From the viewpoint of the improvement in adhesiveness, the ratio (radical generator (C)/thiol groups) is preferably 0.5 or lower, more preferably 0.45 or lower, and particularly preferably 0.4 or lower.
- The content of the amine-based catalyst (D) in the composition used in the present invention is preferably 0.005 parts by mass to 5 parts by mass, more preferably from 0.01 parts by mass to 4 parts by mass, and particularly preferably from 0.05 parts by mass to 3.5 parts by mass, relative to 100 parts of the polythiol compound (A), from the viewpoint of increasing the film strength and the adhesive power by sufficiently promoting the reaction between the polyol compound (A) and the compound (B) having plural epoxy groups.
- As described above, the composition used in the present invention may include optional components (for example, the surface controlling agent (E), the compound that includes a carbon-carbon double bond, or the solvent) in addition to the components (A) to (D). However, from the viewpoint of strongly adhering to rubber, particularly to vulcanized rubber, the total content of the components (A) to (D), excluding solvents, in the composition is preferably 80% by mass or higher, more preferably 90% by mass or higher, still more preferably 95% by mass or higher, and further preferably 98% by mass or higher, with respect to the total amount, excluding solvents, of the composition.
- From the same viewpoint, the total content of the components (A) to (E), excluding solvents, in the composition is preferably 90% by mass or higher, more preferably 95% by mass or higher, still more preferably 99% by mass or higher, and further preferably 100% by mass, with respect to the total amount, excluding solvents, of the composition.
- As described above, the composition used in the present invention is able to exhibit high adhesive power to rubber. Thus, the composition used in the present invention can suitably be used, as a composition for adhesion, in an adhesive particularly suitable for application to rubber or in a layered body that includes a rubber layer and an adhesion layer, as described below. However, the applications of the composition according to the present invention are not limited thereto; for example, colored particles may be incorporated into the composition used in the present invention, in which case the composition may be used as a coating material for imparting decoration.
- The adhesive used in the present invention includes the composition used in the present invention. The adhesive may include components other than the composition used in the present invention, so long as the effect of the present invention is not hindered. However, from the viewpoint of enabling the effect of the present invention to be favorably exerted, the content of the composition in the adhesive is preferably 90% by mass or higher, more preferably 95% by mass or higher, still more preferably 99% by mass or higher, and further preferably 100% by mass, with respect to the total amount, excluding solvents, of the adhesive.
- The layered body according to the present invention includes, in the recited order, a rubber layer, an adhesion layer formed using the composition according to the present invention, and another layer. In other words, the layered body according to the present invention is a layered body (laminated body) which includes plural layers adhered to one another, and in which at least one of the layers is a rubber layer, and in which the rubber layer is adhered to an adjacent layer via an adhesion layer formed using the composition or the adhesive Here, the rubber layer and the other layer are not particularly limited except that they should have an adhesion face with which the adhesion layer contacts; the adhesion face is not limited to a flat plane, and may be a curved face or a face having irregularities. With respect to the rubber layer and the other layer that are adhered via the adhesion layer, the entire adhesion face of the rubber layer and/or the entire adhesion face of the other layer may be adhered via the adhesion layer, or only a part of the adhesion face of the rubber layer and/or only a part of the adhesion face of the other layer may be adhered via the adhesion layer. The layered body according to the present invention may have a configuration in which three or more layers, including a rubber layer, are layered with the adhesion layer(s) according to the present invention disposed therebetween. This configuration is not limited to a configuration in which all of the layers are adhered to one another via the adhesion layer according to the present invention.
- Each of the other layers may be a rubber layer, or a layer other than a rubber layer, such as a glass layer, a metal layer or a resin layer.
- The dimensions of each layer and the number of layers may be selected, as appropriate, in accordance with the purpose.
- The rubber layer may be formed from vulcanized rubber or unvulcanized rubber. The rubber constituting the rubber layer preferably has a carbon-carbon double bond. In this case, it is conceivable that a carbon atom of a carbon-carbon double bond contained in the rubber layer contacting the adhesion layer forms a carbon-sulfur bond with a sulfur atom of a thiol group of the polythiol compound (A) contained in the composition according to the present invention.
- However, it is conceivable that a layered body can be obtained even when the rubber constituting the rubber layer does not have a carbon-carbon double bond. In this case, it is conceivable that a sulfur atom of a thiol group of the polythiol compound (A) and a carbon atom of a carbon-carbon bond chemically binds to each other via a hydrogen abstraction reaction in which the polythiol compound (A) pulls out hydrogen from the main chain formed by carbon-carbon bonds present in the rubber. However, from the viewpoint of improving the adhesive power, it is preferable that the rubber constituting the rubber layer has a carbon-carbon double bond.
- The material of the rubber layer is not particularly limited, and examples thereof include: natural rubber (NR); conjugated diene synthetic rubber, such as polyisoprene synthetic rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), and butyl rubber (IIR); ethylene-propylene copolymer rubber (EPM); ethylene-propylene-diene copolymer rubber (EPDM); and polysiloxane rubber. Materials for the rubber layer, such as those described above, may be used singly or in combination of two or more thereof. Among those described above, natural rubber (NR), and a mixture of natural rubber and a styrene-butadiene copolymer rubber (SBR/NR), are preferable.
- Examples of the other layers than the rubber layer include a glass layer, a metal layer, and a resin layer. Strong adhesion of a metal layer or a resin layer to the rubber layer can be achieved by using the composition according to the present invention.
- Next, a method of producing a layered body using the adhesive used in the present invention (or the composition used in the present invention) is described.
- First, the adhesive is applied to an adhesion face of a rubber layer. Then, after being left to stand for a predetermined period of time, if necessary, an adhesion face of another layer that should face the rubber layer is brought into contact with the face to which the adhesive has been applied (the adhesion face of the rubber layer), to obtain a layered body. In this process, the adhesive may have been applied also to the adhesion face of the other layer that should face the rubber layer.
- Then, curing is performed while a pressure (e.g., pressing) is applied, if necessary, to the obtained layered body in the thickness direction thereof, whereby a layered body can be produced in a favorable manner.
- Alternatively, the adhesive may be applied to an adhesion face of another layer that should face a rubber layer. Then, after being left to stand for a predetermined period of time, if necessary, an adhesion face of the rubber layer is brought into contact with the face to which the adhesive has been applied (the adhesion face of the other layer), to obtain a layered body. In this process, the adhesive may have also been applied to the adhesion face of the rubber layer.
- Then, curing is performed while pressure (e.g., pressing) is applied, if necessary, to the obtained layered body in the thickness direction thereof, whereby a layered body can be produced in a favorable manner.
- When the face to which the adhesive has been applied is left to stand for a predetermined time after the application, the period during which the face is left to stand is preferably from 0 to 30 minutes, and more preferably from 1 to 15 minutes, from the viewpoint of maintaining the shape of the adhesive such that the adhesive would not exude from the layered body at the time of curing.
- When pressure is applied to the layered body, the pressure is preferably from 0 to 5 MPa, more preferably from 0 to 2.5MPa, and particularly preferably from 0 to 1 MPa, from the viewpoint of improving the adhesive power and preventing or suppressing exudation of the adhesive from the layered body. From the same viewpoint, the pressing time is preferably from 5 to 120 minutes, more preferably from 10 to 60 minutes, and particularly preferably from 15 to 45 minutes.
- When the adhesive according to the present invention includes a thermal radical generator as a radical generator, the curing of the adhesive is preferably performed by heating. A temperature at which the thermal radical generator generates radicals efficiently may appropriately be selected as the heating temperature, and the heating temperature is preferably a temperature that is within about ± 30°C from the temperature at which the half-life of the thermal radical generator is one minute.
- When the adhesive includes a photoradical generator as a radical generator, the curing is preferably performed by photoirradiation. A ultraviolet (UV) lamp is preferably used as the light source from the viewpoints of improving the adhesive power and reducing costs. From the same viewpoint, the photoirradiation time is preferably from several seconds to several tens of seconds.
- The present invention is described below in further details by reference to examples. However, the present invention is not limited to the following examples.
- The following materials were used as raw materials.
- Pentaerythritol tetrakis(3-mercaptopropionate) (PEMP): a product manufactured by SC Organic Chemical Co., Ltd.
- Cresol-novolac-type epoxy compound: JER152 (tradename) manufactured by Mitsubishi Chemical Corporation
Bisphenol A-type Epoxy Compound: EP-4100 (tradename) manufactured by ADEKA CORPORATION
Hydrogenated bisphenol A-type epoxy compound: EPOLIGHT4000 (tradename) manufactured by KYOEISHA CHEMICAL Co., Ltd.
Epoxy Compound B-4 illustrated above - t-butyl peroxy-2-ethylhexanoate: PERBUTYL O (tradename) manufactured by NOF CORPORATION
- Triethylene diamine (TEDA)
- Silicone acrylate-based surface controller: SIU2400 (tradename) manufactured by Toyo Chemicals Co., Ltd.
- The total molar number (SH) of thiol groups contained in the polythiol compound (A) was calculated by dividing the addition amount by the theoretical molecular weight, and multiplying the obtained value by the number of thiol groups contained in one molecule of the polythiol compound (A).
- Among the compounds for the component (B), the total molar number (Ep) of epoxy groups contained in JER152 as the component (B) was obtained by calculation based on the method according to JIS K7236:2001. For the other compounds used as the component (B), the total molar number (Ep) of epoxy groups was obtained by dividing the addition amount mentioned above by the theoretical molecular weight, and multiplying the obtained value by the number of epoxy groups contained in one molecule of the component (B).
- Rubber (having a length of 100 mm, a width of 25 mm, and a thickness of 3 mm) was produced from the formulation indicated in the following Table 1.
Table 1 Type of Rubber NR/SBR NR Formulation NR 15 100 SBR 85 - Carbon Black 50 50 Stearic Acid 2 2 Anti-aging Agent 1 1 Zinc Oxide 3 3 Vulcanization Accelerator 1 0.4 0.4 Vulcanization Accelerator 2 0.2 0.2 Sulfur 1.4 1.4 *Numbers in the table indicate parts by mass - The specifics of the individual components noted in Table 1 are as follows.
- Natural Rubber (NR): RSS#3
Styrene-butadiene Copolymer Rubber (SBR):
JSR1500 (tradename) manufactured by JSR CORPORATION
Anti-aging Agent: N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (NOCRAC 6C (tradename) manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.) - Vulcanization Accelerator 1:
1,3-diphenylguanidine (NOCCELER D (D-P) (tradename) manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.) - Vulcanization Accelerator 2:
di-2-benzothiazolyl disulfide (NOCCELER DM-P (DM) (tradename) manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.) - In Examples 1 to 9 and Comparative Examples 1 to 7, in which the NR/SBR was used as rubber, the relationship between the adhesive power and the ratio (Ep/SH) of the total molar number of epoxy groups contained in the addition amount of the compound (B) having plural epoxy groups to the total molar number of thiol groups contained in the addition amount of the polythiol compound (A) was studied by changing the ratio (Ep/SH).
- In Examples 10 to 14 and Comparative Examples 8 to 12, in which the NR was used as rubber, the relationship between the adhesive power and the ratio (Ep/SH) was studied in the same manner as described above, except that the rubber (the NR/SBR), which was employed in Examples 1 to 9 and Comparative Examples 1 to 7, was replaced by another rubber (the NR).
- The Examples and Comparative Examples are specifically described below.
- Ingredients were mixed according to the formulation indicated in Table 2 (the number for each ingredient represents the parts by mass of non-volatile portion), to obtain a composition, and the composition was employed as an adhesive. The NR/SBR was used as the rubber.
- The obtained adhesive was applied, in a thickness of 30 µm, to two rubber sheets (rubber substrates), and the coated faces were adhered to each other and curing was performed, as a result of which a layered body was prepared. The curing was performed by maintaining the adhered bodies at a temperature of 150°C while applying a pressure of 0.05 MPa for 20 minutes. Then, the adhesive power of the cured body of the adhesive (the adhesion layer) was measured as described below. The results thereof (evaluation results) are indicated in Table 2.
- The opposite ends of the adjacent rubber substrates in the layered body were pulled away from each other (in the directions normal to the principal faces of the rubber substrates, the directions forming an angle of 180°) at a pulling rate of 50 mm/min., and the delamination strength (N/25mm) was measured and used as an indicator of the adhesive power.
- With respect to the adhesive power, a delamination strength of 100N/25mm or greater indicates that a sufficient adhesive power at a level at which the rubber substrate breaks before delamination occurs is obtained. The delamination strength is preferably 300N/25mm or greater. In contrast, a delamination strength of less than 100N/25mm indicates that the reaction at the interface between the rubber substrate and the adhesive has not proceeded sufficiently, and delamination would occur at the interface or the adhesive itself would undergo cohesive failure due to insufficient cohesive force of the adhesive. Occurrence of such a phenomenon indicates that the adhesive power is insufficient.
- Ingredients were mixed according to the formulation indicated in the following Table 3 (the number for each ingredient indicating the parts by mass of non-volatile portion), to obtain a composition, and the obtained composition was used as an adhesive.
- The obtained adhesive was cured in the same manner as described above, and the adhesive power of the cured body of the adhesive was measured in the same manner as described above. The NR was used as the rubber. The results thereof (the evaluation results) are indicated in Table 3.
Table 2 Adhesive Composition Composition Epoxy Groups/ Thiol Groups Component (C)/Thiol Groups Evaluation Component (A) Component (B) Component (C) Component (D) Component (E) Adhesive Power PEMP JER152 EP-4100 EPOLIGHT 4000 B-4 PERBUTYL O TEDA SIU2400 (% by mass) (% by mass) (% by mass) (% by mass) (% by mass) (% by mass) (% by mass) (% by mass) (Molar Ratio) (Molar Ratio) (N/25mm) Comparative Example 1 50.45 21.67 - - - 26.79 0.08 1.01 0.30 0.3 8.24 Comparative Example 2 49.49 - 23.08 - - 26.28 0.16 0.99 0.30 0.3 4.89 Comparative Example 3 47.05 - - 26.56 - 24.98 0.47 0.94 0.30 0.3 8.69 Comparative Example 4 42.67 - - - 33.12 22.66 0.70 0.85 0.30 0.3 20.91 Example 1 34.95 - - - 45.23 18.56 0.56 0.70 0.50 0.3 285.13 Example 2 33.50 47.98 - - - 17.79 0.06 0.67 1.00 0.3 138.88 Example 3 31.97 50.36 - - - 16.98 0.05 0.64 1.10 0.3 254.71 Example 4 26.18 - - 59.14 - 13.90 0.26 0.52 1.20 0.3 170.59 Example 5 29.24 - 54.55 - - 15.53 0.10 0.58 1.20 0.3 224.10 Example 6 29.29 54.52 - - - 15.55 0.05 0.59 1.30 0.3 212.07 Example 7 27.02 58.05 - - - 14.35 0.04 0.54 1.50 0.3 290.53 Example 8 25.73 - 60.02 - - 13.66 0.08 0.51 1.50 0.3 364.02 Example 9 22.97 - 64.29 - - 12.20 0.08 0.46 1.80 0.3 150.31 Comparative Example 5 22.64 64.85 - - - 12.02 0.04 0.45 2.00 03 1.00 Comparative Example 6 18.78 - - 70.68 - 9.97 0.19 0.38 2.00 0.3 3.00 Comparative Example 7 14.83 - - - 76.76 7.87 0.24 0.30 2.00 0.3 8.34 * In the table, "-" indicates that the component is not included. Table 3 Adhesive Composition Composition Epoxy Groups/ Thiol Groups Component (C)/Thiol Groups Evaluation Component (A) Component (B) Component (C) Component (D) Component (E) Adhesive Power PEMP JER152 EP-4100 EPOLIGHT 4000 B-4 PERBUTYL O TEDA SIU2400 (% by mass) (% by mass) (% by mass) (% by mass) (% by mass) (% by mass) (% by mass) (% by mass) (Molar Ratio) (Molar Ratio) (N/25mm) Comparative Example 8 50.45 21.67 - - - 26.79 0.08 1.01 0.30 0.3 1.60 Comparative Example 9 49.49 - 23.08 - - 26.28 0.16 0.99 0.30 0.3 3.33 Comparative Example 10 47.05 - - 26.56 - 24.98 0.47 0.94 0.30 0.3 1.51 Comparative Example 11 38.42 - - - 39.78 20.40 0.63 0.77 0.40 0.3 114.72 Example 10 34.95 - - - 45.21 18.56 0.58 0.70 0.50 0.3 180.51 Example 11 33.50 47.98 - - - 17.79 0.06 0.67 1.00 0.3 205.92 Example 12 32.16 - 50.01 - - 17.08 0.11 0.64 1.00 0.3 109.62 Example 13 29.24 - 54.55 - - 15.53 0.10 0.58 1.20 0.3 120.98 Example 14 26.01 59.61 - - - 13.82 0.04 0.52 1.60 0.3 103.50 Comparative Example 12 14.83 - - - 76.76 7.87 0.24 0.30 2.00 0.3 0.55 * In the table, "-" indicates that the component is not included. - As indicated in the tables above, the adhesive power in Examples 1 to 14 was high due to the inclusion of the components (A) to (D), and the ratio (Ep/SH) of the total molar number of epoxy groups contained in the component (B) to the total molar number of thiol groups contained in the component (A) being from 0.50 to less than 2.00.
- In contrast, the adhesive power in Comparative Examples 1 to 12 was low as a result of the ratio (Ep/SH) being outside the range defined in the present invention.
- The composition according to the present invention can suitably be used in an adhesive suitable for, particularly, application to rubber, and in a layered body including a rubber layer and an adhesion layer. However, the applications of the composition according to the present invention are not limited thereto, and the composition can also be used, for example, as a coating material to which colored particles are incorporated, and which is used for imparting decoration.
Claims (13)
- A layered body comprising a rubber layer and an adhesion layer, the adhesion layer being formed using a composition including:a polythiol compound;a compound having plural epoxy groups;a radical generator; andan amine-based catalyst,wherein a ratio (Ep/SH (epoxy groups/thiol groups)) of a total molar number (Ep) of epoxy groups contained in the compound having plural epoxy groups to a total molar number (SH) of thiol groups contained in the polythiol compound is 0.50 or higher but lower than 2.00,wherein the radical generator is a thermal radical generator comprising a peroxide,a ratio of a total molar number of carbon-carbon double bonds contained in optional carbon-carbon double bond-containing compounds contained in the composition relative to the total molar number of thiol groups contained in the polythiol compound contained in the composition (carbon-carbon double bonds/thiol groups) is lower than 0.4,the total molar number (SH) of thiol groups contained in the polythiol compound is obtained by multiplying the molar number of the polythiol compound by the number of thiol groups contained in one molecule of the polythiol compound,the total molar number (Ep) of epoxy groups contained in the compound having plural epoxy groups is obtained by dividing the content of the compound having plural epoxy groups by a theoretical molecular weight of the compound having plural epoxy groups, and multiplying the obtained value by the number of epoxy groups contained in one molecule of the compound having plural epoxy groups, andthe total molar number of carbon-carbon double bonds contained in the carbon-carbon double bond-containing compound contained in the composition is obtained by multiplying the molar number of the carbon-carbon double bond-containing compound contained in the composition by the number of carbon-carbon double bonds contained in one molecule of the carbon-carbon double bond-containing compound.
- The layered body according to claim 1, wherein the polythiol compound is a primary thiol.
- The layered body according to claim 1 or claim 2, wherein the polythiol compound has three or more thiol groups in one molecule thereof.
- The layered body according to any one of claims 1 to 3, wherein the polythiol compound has a molecular weight of from 200 to 3000.
- The layered body according to any one of claims 1 to 4, wherein the polythiol compound is selected from the group consisting of: a polythiol in which a portion other than the thiol groups is an aliphatic hydrocarbon; a polythiol obtainable by replacing halogen atoms of a halohydrin adduct of an alcohol by thiol groups; a polythiol that is a hydrogen sulfide reaction product of a polyepoxide compound; a thioglycolic acid ester obtainable by an ester-forming reaction between a polyhydric alcohol having from 2 to 6 hydroxyl groups in a molecule thereof and thioglycolic acid; a mercapto fatty acid ester obtainable by an ester-forming reaction between a polyhydric alcohol having from 2 to 6 hydroxyl groups in a molecule thereof and a mercapto fatty acid; a thiol isocyanurate compound obtainable by a reaction between an isocyanurate compound and a thiol; a thiol that includes a polysulfide group; a silicone modified with thiol groups; and silsesquioxane modified with thiol groups.
- The layered body according to any one of claims 1 to 5, wherein the compound having plural epoxy groups has an epoxy equivalent weight of 3000 or less.
- The layered body according to any one of claims 1 to 6, wherein the compound having plural epoxy groups is selected from the group consisting of an aromatic epoxide having a ring structure other than a glycidyl group, an alicyclic epoxide having a ring structure other than a glycidyl group, and modified products thereof.
- The layered body according to any one of claims 1 to 7, wherein the compound having plural epoxy groups is an aromatic epoxide having two or more aromatic rings.
- The layered body according to any one of claims 1 to 8, wherein the amine-based catalyst is a diamine.
- The layered body according to any one of claims 1 to 9, wherein a ratio of a total molar number of the radical generator to a total molar number of thiol groups contained in the polythiol compound (radical generator/thiol groups) is from 0.025 to 0.5.
- The layered body according to any one of claims 1 to 10, wherein the ratio (Ep/SH (epoxy groups/thiol groups)) of the total molar number (Ep) of epoxy groups contained in the compound having plural epoxy groups to the total molar number (SH) of thiol groups contained in the polythiol compound is from 0.50 to 1.80.
- The layered body according to any one of claims 1 to 11, further comprising a surface controller.
- The layered body according to any one of claims 1 to 12, further comprising another layer, wherein the rubber layer, the adhesion layer, and another layer are arranged in this order.
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2014
- 2014-12-22 EP EP14873530.1A patent/EP3088436B1/en active Active
- 2014-12-22 WO PCT/JP2014/083973 patent/WO2015098874A1/en active Application Filing
- 2014-12-22 CN CN201480067881.7A patent/CN105814109B/en active Active
- 2014-12-22 JP JP2015554897A patent/JP6429797B2/en active Active
- 2014-12-23 US US14/580,475 patent/US9637666B2/en active Active
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Also Published As
Publication number | Publication date |
---|---|
EP3088436A1 (en) | 2016-11-02 |
US9637666B2 (en) | 2017-05-02 |
JP6429797B2 (en) | 2018-11-28 |
JPWO2015098874A1 (en) | 2017-03-23 |
CN105814109A (en) | 2016-07-27 |
WO2015098874A1 (en) | 2015-07-02 |
EP3088436A4 (en) | 2016-11-02 |
US20150175857A1 (en) | 2015-06-25 |
CN105814109B (en) | 2018-04-27 |
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